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IOP PUBLISHING Phys. Scr. T152 (2013) 000000 (4pp)

PHYSICA SCRIPTA UNCORRECTED PROOF

Optical luminescence studies of the xanthate adsorption layer at the solidliquid interface
R Todoran, D Todoran and Zs Szak acs
Technical University of Cluj Napoca, North University Centre of Baia Mare, Street V Babe s, nr 62/A, RO-430083, Baia Mare, Maramure s, Romania E-mail: todoran radu@yahoo.com

Received 18 August 2012 Accepted for publication 21 January 2013 Published xxx Online at stacks.iop.org/PhysScr/T152/000000 Abstract In this paper, we propose optical luminescence as a method for the evaluation of the kinetics of adsorption processes to calculate the time required to achieve the dynamic balance of the thin layers formed at the mineralxanthate solution interface. The method is based on the measurement of the intensity for the integral optical radiation obtained from the mineralxanthate thin layer, which is stimulated with a monochromatic pulsating optical signal, as a function of time. The luminescence was studied for the galena, sphalerite and chalcopyrite minerals with sodium amyl and sodium isobutyl xanthates, for different concentrations of the solutions and different pH values under constant temperature. Using the said method, information was gained on the kinetics of the adsorption of xanthates. Good correlation with the sequential (radiometric) investigation methods was noticed. A better measurement of the time to achieve equilibrium in the formation of the adsorption layer was also obtained. PACS numbers: 68.03.g, 68.43.Mn, 68.43h (Some gures may appear in colour only in the online journal)

1. Introduction
In the study of the chemisorption and physical adsorption mechanisms one must take into account the dynamic processes that take place at the interface level [13]. The boundary surfaces in liquids and solutions have homogeneous characteristics for different regions. In the case of solid surfaces, the position of the atoms is xed and the surface has a complex, inhomogeneous structure. This fact underlines the great interest in the study of adsorption processes at solid surfaces, especially for industrial and technological processes, such as mineral otation, based on this phenomenon at the solidliquid interface. The physical and chemical adsorption processes of the xanthate molecules at the solidliquid interface represent a condition to modify the oatability of many non-ferrous minerals in the process of separating the metallic compounds from the gangue [46].
0031-8949/13/000000+04$33.00

In this paper, we propose optical luminescence as a method in the evaluation of the kinetics of adsorption processes, to calculate the time to achieve dynamic balance for the thin layers that are formed. Up to recent times, the study of solidliquid interfaces was mainly done to establish isothermal equations, but true thermodynamic equilibrium was infrequent. These were statistical methods and were not applied for in situ evaluations [7]. Knowledge of the kinetic mechanisms of adsorption desorption is linked to understanding the related processes, which take place at the level of the liquid or solid phase, and play an important role in the characterization of the interface phenomena. There are a few models for the kinetics of the interface processes with a different degree of generalization. In [8] a mathematical algorithm is proposed. It takes into account the adsorptiondesorption processes and the diffusion in the liquid phase, yet without a clear particularization to specic cases of the solidliquid interfaces.
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2013 The Royal Swedish Academy of Sciences Printed in the UK

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2. Method and samples

The optical luminescence method is based on the determination of the integral optical radiation from the adsorption layer stimulated by a pulsing monochromatic signal. The experimental determinations conducted were accompanied by radiometric ones. Radiometric analysis requires that some molecules in the xanthate should be marked with the radioisotope 35 S. The main advantage of the optical luminescence is that it allows a continuous in situ evaluation of the interface processes. The radiometric method is also reliable, but special laboratory facilities are required to handle the radioisotopes. As it is a sequential method, the determinations should be made in time intervals or only at the stop of the interface process [9]. The optical luminescence determinations were made during an interval of 35 min, after which the equilibrium was reached in the adsorptiondesorption processes at the interface level. During the experimental determinations, we worked with the following types of mineral: galena, sphalerite, activated sphalerite and chalcopyrite. The types of xanthates used were sodium amyl xanthate (C6 H16 NaOS2 ) and sodium isobutyl xanthate (C5 H9 NaOS2 ) in the following concentrations: 10, 25, 50, 100 and 3000 mg l1 . One must point out that, from the analysed minerals, sphalerite in its natural state has low adsorption capacity. That is the reason why, in most cases, it undergoes an activation process before otation in the industrial regime. The activation of sphalerite is a chemical procedure that is applied to the surface of the mineral and facilitates the bond of the collector reagents on it. That is done by increasing the number of oriented adsorption centres of the collector reagent at the surface of the minerals by chemisorptions or exchange reactions. In most cases, the sphalerite is activated using copper sulphate. The mechanism of activation with copper sulphate, which facilitates the bond of the xanthogenate, is ZnS ZnS + Cu2+ = + Zn2+ . ZnS CuS (1)

After this treatment is applied to the surface of the mineral, more powerful anodic regions are formed, facilitating the attachment of the polar group of the collector. Using electron spin resonance it was noticed that the interaction of the Cu2+ ion with the lattice of the sphalerite ZnS can take place through the capture of one lattice electron, followed by the integration of the formed monovalent Cu+ in the lattice, based on the following mechanism [10]: Zn|() . . . Zn2+ + Cu2+ ZnS|+ . . . Cu+ + Zn2+ . (2)

important role in the stability of the xanthate, and especially because of its direct inuence on the development of the adsorption phenomena. The oatability is maximal in the above-mentioned domain of the pH. For pH values lower than 5, oating and adsorption are almost non-existent, while increasing the pH to values higher than 10 induces very low variations in the processes. The working temperature was set to an exact 18 C using a thermostat. This temperature was chosen because it is the temperature most likely to be present in the industrial process [12]. To ensure a high measuring reproducibility, we xed the volume of each xanthate solution used in every kinetic determination to 2 ml. To check the reproducibility of determinations, multiple determinations were made for the same mineral sample while the volume of the xanthate solution remained xed to the aforementioned value. The surface chemical abrasion was made with a spray of pickle liquor. An air spray was used to dry the surface. The mineral samples were positioned with the polished surface in a perfectly horizontal position, and the xanthate volume was placed on this surface. The horizontal alignment of the mineral surfaces was checked using two parallel beams of light, originating from two coplanar horizontal HeNe lasers. The experimental installation for the in situ measurements of the optical luminescence radiation at the mineralxanthate solution interface is presented in gure 1. The laser used in the experimental setup was a pulsing nitrogen laser of the LGI-21 type with a pulsing frequency of 25 Hz and the wavelength of the emitted radiation being = 337.1 nm (3.68 eV). It has a power of 1.6 kW, and the length of a pulse is = 108 s. The laser radiation of this wavelength should stimulate a layer of at most 2025 , a value resulting from the band absorption coefcients. The width of the domain of laser measurements was 1 Hz; consequently, the frequency band for the measurements was 25 1 Hz. The selective amplier at 25 Hz of the type U2-8 was put to resonance with the signal from the photomultiplier. The used electronic photomultiplier was of the FME-51 type. The photocathode is multi-alkaline, with a known sensitivity in the spectral interval of 290900 nm, and with low levels for the induced noise signal. This essential characteristic is due to the relatively large surface of the photocathode. The mirror reects the UV and total radiation and concentrates the light beam on the sample to the mineralxanthate surface. The laser stabilizer gives good frequency stability to the laser radiation emitted in the pulsating system. The BS-8 optical lter blocks the laser radiation from reaching the photomultiplier.

3. Results and discussion

The experimental determinations were made using the integral luminescence radiation on the full sensibility spectrum of the photocathode since work was undertaken with molecular species that have a broad frequency domain for it. We can study the formation of the xanthate adsorption layers on the mineral surface from the voltagetime graphs obtained from experimental determinations, this phenomenon being strongly connected to the modication of the optical luminescence.
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One can note the ionic exchange between the Cu2+ ions and the Zn2+ ions from the lattice followed by the reduction of Cu2+ to Cu+ and its integration in the lattice. Thus, the number of Cu2+ ions in the solution drops, while the number of Zn2+ ions is increased by the same amount [11]. In the activation process the surface of sphalerite was treated with a CuSO4 solution of 310 g l1 for 30 min. The xanthate solutions used had the following pH values: 7, 8, 9 and 10. Different pH values were used due to its

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Nitrogen laser LGI - 21

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St RS-22 St - 100 FME-51

U2-8

12 6

10

9 1 7 8 5 4
Figure 1. Block scheme of the experimental installation for the in situ measurements of the optical luminescence radiation at the mineralxanthate solution interface. 1laser stabilizer; 2pulsing laser; 3reection mirror for the laser radiation; 4mineral; 5xanthate solution; 6laser radiation; 7solidliquid interface; 8luminescence radiation; 9optical lter; 10photomultiplier; 11stabilizer for the photomultiplier; 12selective amplier.

Figure 2. Intensity for the luminescence radiation as a function of time for (a) amyl xanthate and (b) isobutyl xanthate and chalcopyrite for pH = 7 and solution concentrations of 10 mg l1 (long-dashed green), 25 mg l1 (dashed violet), 50 mg l1 (square-dotted blue), 100 mg l1 (circle-dotted orange) and 3000 mg l1 (solid blue). The red circles are the rescaled result of the radiometric measurements.

During the adsorption process, we obtained the voltage characteristics proportional to the intensity of luminescence radiations from the optically stimulated surfaces. The parameters modied during the experimental determinations were the type of mineral, the type of xanthate, the concentration and the pH of the xanthate solution. In each set of determinations only one of these parameters was varied, while the other three were kept constant. The experimental results were compared with the radiometric ones, which are extensively used in determinations of the xanthate content in the adsorbed layers on mineral surfaces. As usual 35 S was the radioactive marker. The xanthate obtained from the solution was oxidized with alkaline permanganate to sulphate, and it was precipitated as barium sulphate. The radioactivity of the dried precipitate was measured knowing that 35 S is a low-energy beta emitter and that its half-life is 87.1 days. The good correlation between the rescaled radiometric results and the optical determinations can be observed in gure 2.
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The luminescence curves indicate a slightly higher rate of adsorption of the amyl xanthate than of the isobutyl xanthate, while, after the equilibrium is reached, the adsorbed quantities are almost equal. The highest adsorption for the different minerals, as can be observed in gure 3, is in the case of chalcopyrite, then galena and activated sphalerite. The lowest adsorption was noticed for the natural, non-activated sphalerite [5, 13, 14]. The concentration of xanthate collector reagents adsorbed on the mineral surface increases rapidly in the rst few minutes of contact and reaches a dynamic equilibrium after 2530 min. Chalcopyrite presents the most intense adsorption properties for these reagents; it is followed by galena and sphalerite. The adsorption properties of sphalerite in its natural, non-activated state are very poor, as can be seen in gure 3. The variation of the solutions pH changes the adsorption properties of the minerals, as can be seen in gure 4. The decrease of the adsorption with the increase of the pH can be explained by the high concentration of OH ions. These ions

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These results were obtained by sequential methods and can also be deduced from our optical luminescence studies.

4. Conclusions
In this paper, optical luminescence was presented as an in situ evaluation method for the kinetics of the adsorption processes at the mineralxanthate solution interfaces. The luminescence was studied for the galena, sphalerite and chalcopyrite minerals with sodium amyl xanthate and sodium isobutyl xanthate. We noticed that amyl xanthate has a marginally higher adsorption rate than the isobutyl variation. The increase in concentration for the xanthate solutions does inuence in a nonlinear way the adsorption process: a high increase of the solution concentration is reected in a low increase of the adsorption coefcient. The highest adsorption is obtained for chalcopyrite; that is followed closely by galena and activated sphalerite, while natural sphalerite has low adsorption properties. The inuence of the pH of the xanthate solution was also dealt with; an increase in the pH level was associated with a decreasing tendency of the adsorption. The time to achieve dynamic equilibrium was determined to be 2530 min in all of our cases. A good correlation with radiometric methods was also found. The xanthate adsorption studies on sulphurous minerals led to a better understanding of the dynamics of otation processes; they had a direct technological inuence on the optimization of the time allocated to these processes.

Figure 3. Intensity for the luminescence radiation as a function of time for amyl xanthate solution and chalcopyrite (solid green), galena (dotted violet), activated sphalerite (dashed blue) and sphalerite (long-dashed orange) with a xanthate-solution concentration of 50 mg l1 and pH = 7.

Figure 4. Intensity for the luminescence radiation as a function of time for amyl xanthate solution and chalcopyrite with a solution concentration of 50 mg l1 for pH = 7 (solid green), pH = 8 (dotted violet), pH = 9 (dashed blue) and pH = 10 (long-dashed orange).

References
[1] Isobe Y I T and Senna M 1996 J. Phys. Chem. Solids 57 3739 [2] Sooklal K, Cullum B S, Angel S M and Murphy C J 1996 J. Phys. Chem. B 100 45515 [3] Huang J, Yang Y, Xue S, Yang B, Liu S and Shen J 1997 Appl. Phys. Lett. 70 23357 [4] Todoran R and Todoran D 2008 Phys. Mac. 57/59 3540 [5] Todoran R and Sharkany J 1999 Proc. SPIE 3687 268 [6] Hough D B and Rendall H M 1983 Adsorption from Solution at the Solid/Liquid Interface ed D G Part and C H Rochester (London: Academic) pp 1520 [7] Kralchevsky P A, Radkov S Y and Deukov D N 1993 J. Colloid Interface Sci. 161 3615 [8] Shibata C T and Lenhoff A M 1992 J. Colloid Interface Sci. 148 485507 [9] Leja J 1982 Surface Chemistry of Froth Flotation (New York: Plenum) 205 [10] Barbus A, Sinko I and Cojocaru L N 1977 Rev. Roum. Phys. 22 667 [11] Sinco I, B arbu s A, Baican R and Cojocaru L N 1979 Studii s i Cercet ari de Fizic a vol 10 (Bucuresti: Acad. RSR) pp 112930 [12] Huber-Panu I 1930 Uber den Einfuss der Temperatur auf die Flotation (Freiberg: E. Mauchisch) pp 1078 [13] Todoran R and Todoran D 1998 Innovations in Mineral and Coal Processing ed S Atak, G Onal and M Sabri Celik (Rotterdam: A.A. Balkena) pp 1837 [14] Todoran R, Todoran D and Stan O 1997 Balkan. Phys. Lett. 5 238992 [15] Glembotchii O V, Mitrofanov S I and Davidova L M 1983 Tsvetnie Metalli 11 1167 [16] Tipmann R N and Leja J 1975 Colloid Polym. Sci 253 410 [17] Markovic Z, Milosevic S, Mantonijevic M and Stanojlovic R 1997 Balkan Conf. on Mineral Processing Vatra Dornei vol II 2258 4

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have a depressing role; they compete with the ions from the collector reagents in the adsorption process on the surface of the sulphurous minerals [15]. Sphalerite is the least inuenced by these variations. Results similar to the ones presented in this paper were obtained by Tipman (Germany, 1975) [16] and by the team led by Markovic (Yugoslavia, 1997) [17]. Markovic used amyl xanthate concentrations of 3 105 and 6 105 mol l1 , where the pH was 7, 8, 9, 10 and 11. The method was UVVIS and BET spectroscopy with sequential determinations, leading to the conclusion that the adsorption coefcient at the interface, expressed in mol m2 , drops when the pH increases. The samples used were chalcopyrite minerals dried in the oven; the pH was varied using calcium hydroxide. Tipman used a Beckman DU-55-UVVIS spectrophotometer to determine the concentration of the residual xanthate in the solution after the adsorption process ended on the chalcopyrite surface, with rigorously known initial concentrations of the xanthate solutions. The adsorption ratio was computed using the concentration difference of the xanthate solutions before and after the adsorption process. The clear conclusion drawn by Tipman is that of the nonlinear dependence between the increase in the xanthate solution concentration and the adsorption ratio, with a low increase of adsorption at high concentration changes in the solution.

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